Factors that influence singlet oxygen formation vs. ligand substitution for light-activated ruthenium anticancer compounds

Abstract

This review focuses on light-activated ruthenium anticancer compounds and the factors that influence which pathway is favored. Photodynamic therapy (PDT) is favored by π expansion and the presence of low-lying triplet excited states (e.g. ³MLCT, ³IL). Photoactivated chemotherapy (PACT) refers to light-driven ligand dissociation to give a toxic metal complex or a toxic ligand upon photo substitution. This process is driven by steric bulk near the metal center and weak metal-ligand bonds to create a low-energy ³MC state with antibonding character. With protic dihydroxybipyridine ligands, ligand charge can play a key role in these processes, with a more electron-rich deprotonated ligand favoring PDT and an electron-poor protonated ligand favoring PACT in several cases.

Keywords: Anticancer; Diimine ligands; Photoactivated chemotherapy; Photochemistry; Photodissociation; Photodynamic therapy; Photosubstitution; Protic ligands; Ruthenium; pH responsive.